JP2008145830A - Method for manufacturing display device and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a display device by which a display device having excellent durability (sealability) and display unevenness resistance characteristics can be obtained without giving damage to electrodes, and to provide a display element of an electrodeposition system and electrochromic system obtained by the same. <P>SOLUTION: The method of manufacturing the electrochemically operating display includes: forming an electrolytic layer 4 on one electrode 2 of a counter electrode by using an electrolyte, the electrolyte having a high polymer binder and a spacer 3; and forming the display element by sticking together the another one electrode of the counter electrode, wherein the average grain size of the spacer 3 and the film thickness of the electrolytic layer are substantially equal and a layer of a thermosetting resin or photosetting resin is so formed as to surround the outer periphery of the electrolytic layer 4; in addition, a pillar 7 is formed between the electrolytic layer and the layer of the thermosetting resin or the photosetting resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a display element having improved durability (sealing property) and display unevenness resistance, and an electrodeposition type and electrochromic type display element obtained thereby.

  In recent years, with the increase in the operating speed of personal computers, the spread of network infrastructure, the increase in capacity and price of data storage, information such as documents and images previously provided in printed materials such as paper has become easier and more electronic. Various methods of obtaining as information and browsing as electronic information have been proposed.

  As a means for browsing such electronic information, conventional liquid crystal displays and CRTs, and in recent years, light-emitting types such as organic electroluminescence displays are mainly used. However, particularly when electronic information is document information, it is relatively long. It is necessary to keep an eye on this browsing means over time, and these actions are not necessarily human-friendly means. Generally, as a disadvantage of light-emitting displays, eyes flicker due to flickering, inconvenient to carry, limited reading posture In addition, it is known that it is necessary to adjust the line of sight to a still screen, and that power consumption increases when read for a long time.

  As one of the display means to compensate for these disadvantages, a reflection type display (memory type) that does not consume power for image retention using external light is known. However, it has sufficient performance for the following reasons. It ’s hard to say.

  That is, the method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40% and is difficult to display white, and many of the manufacturing methods used for producing the constituent members are not easy. In addition, the polymer dispersed liquid crystal requires a high voltage and utilizes the difference in refractive index between organic substances, so that the resulting image has insufficient contrast. In addition, the polymer network type liquid crystal has problems such as high voltage and the necessity of a complicated TFT circuit for improving the memory performance. In addition, a display element based on electrophoresis requires a high voltage of 10 V or more, and is concerned about durability due to aggregation of electrophoretic particles.

  As a display method for solving the drawbacks of each of the above-mentioned methods, an electrochromic display element (hereinafter abbreviated as EC method) and an electrodeposition method (hereinafter abbreviated as ED method) using dissolution precipitation of a metal or a metal salt. Display elements are known. The EC method is capable of full-color display at a low voltage of 3 V or less, has a simple cell configuration and has excellent white display quality, and the ED method can also be driven at a low voltage of 3 V or less and is simple. With a simple cell configuration, there are advantages such as excellent black and white contrast and black quality, and various methods have been disclosed (for example, see Patent Documents 1 to 5).

  As a result of a detailed study of the techniques disclosed in the above-mentioned patent documents, the present inventor has found that display unevenness occurs in long-term use in the prior art. Means for solving this display unevenness include gelation of the electrolyte and increase in viscosity with a polymer binder, but when a gel-like electrolyte or high-viscosity electrolyte is used, if the display size increases to some extent, It is not possible to apply a known method for manufacturing a display element such as an LCD as it is.

For example, it is difficult to inject a gel-like electrolyte or a high-viscosity electrolyte into a cell with a liquid crystal injection method that has been conventionally known as an LCD manufacturing method, and has recently become widespread as a manufacturing method for large LCDs. The liquid crystal dropping method is a method suitable for filling a gel electrolyte or a high-viscosity electrolyte into the cell, but no effective means for determining the gap between the counter electrodes has been found. The gap determination by the photo spacer cannot increase the aspect ratio from the viewpoint of the durability of the spacer, and as a result, there arises a problem that the aperture ratio of the display area is lowered. As another means, there is a method in which a spacer for determining a gap is mixed in the electrolyte, and the electrolyte layer is dropped by a dispenser to form an electrolyte layer. In this case, the electrolyte is used when the other counter electrode is bonded. At the same time, the spacer moves on the electrode, resulting in damage to the electrode surface, and at the same time, the sealing agent that is not completely cured and the electrolyte layer are in contact with each other, so that the curability and adhesion of the sealing agent are lowered. It was found that the problem occurred.
WO2004 / 068231 Specification WO 2004/066773 specification U.S. Pat. No. 4,240,716 Japanese Patent No. 3428603 JP 2003-241227 A

  The present invention has been made in view of the above problems, and its object is to provide a method for manufacturing a display element that can provide a display element excellent in durability (sealability) and display unevenness resistance without damaging the electrodes. Another object is to provide an electrodeposition type and electrochromic type display element obtained thereby.

  The above object of the present invention is achieved by the following configurations.

  1. An electrochemical method in which an electrolyte contains a polymer binder and a spacer, an electrolyte layer is formed on one electrode of the counter electrode using the electrolyte, and the other electrode of the counter electrode is bonded to form a display element In the method of manufacturing a display element that operates at the same time, when the other electrode of the counter electrode is bonded, the average particle diameter of the spacer is substantially equal to the film thickness of the electrolyte layer. A thermosetting resin or photocurable resin layer is formed so as to surround the outer periphery, and a pillar is formed between the electrolyte layer and the thermosetting or photocurable resin layer. A method for manufacturing a display element.

  2. 2. The method of manufacturing a display element according to 1 above, wherein at least two pillars are formed between the electrolyte layer and a thermosetting resin or photocurable resin layer.

  3. 3. The method for manufacturing a display element according to 1 or 2, wherein the distance between the counter electrodes is determined by an average particle diameter of a spacer contained in the electrolyte layer.

  4). 4. The method for manufacturing a display element according to any one of 1 to 3, wherein a distance between the counter electrodes is determined by a height of the pillar.

  5. 5. The method for manufacturing a display element according to any one of claims 1 to 4, wherein an average particle diameter of a spacer contained in the electrolyte layer is substantially equal to a maximum height of the pillar.

  6. When the two counter electrodes are bonded together, the film thickness of the thermosetting resin or photocurable resin layer is larger than the height of the pillar, any one of 1 to 5 above The manufacturing method of the display element of description.

  7. The said thermosetting resin or photocurable resin which overflowed when the said counter electrode was bonded together is trapped between two adjacent pillars, The said any one of 2-6 characterized by the above-mentioned. A method for manufacturing a display element.

  8). 8. The method of manufacturing a display element according to any one of 1 to 7, wherein a method of forming an electrolyte layer on one electrode of the counter electrode using the electrolyte is a screen printing method.

  9. 9. The method for manufacturing a display element according to any one of 1 to 8, wherein an average particle size of the spacer is 10 μm or more and 50 μm or less.

  10. 10. The method for manufacturing a display element according to any one of 1 to 9, wherein the polymer binder is a butyral resin.

  11. 11. The method for manufacturing a display element according to any one of 1 to 10, wherein the electrolyte layer contains a cyclic carboxylic acid ester as a solvent.

  12 12. The method for producing a display element according to 10 or 11, wherein the butyral resin has an average degree of polymerization of 300 or more and 1000 or less.

  13. 12. The method for producing a display element according to 10 or 11, wherein the butyral resin has an average degree of polymerization of 400 or more and 800 or less.

  14 In the butyral resin, the number of PVA groups represented by the following (A) is 1) the PVA group, 2) the PVAc group represented by the following (B), and 3) the PVB group represented by the following (C). 14. The method for manufacturing a display element according to any one of 10 to 13, wherein the total number is 15% or more and 25% or less.

[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. ]
15. 15. The method for manufacturing a display element according to any one of 10 to 14, wherein a mass ratio of a solvent and a butyral resin constituting the electrolyte layer is in a range of 10: 1 to 2: 1.

  16. 16. The method for manufacturing a display element according to any one of 1 to 15, wherein the electrolyte layer contains a white scatterer.

17. 17. The method for manufacturing a display element according to 16, wherein the white scattering material is titanium dioxide whose surface is modified with at least one selected from SiO ₂ , Al ₂ O ₃ and an organic material.

  18. 18. A display element manufactured by the method for manufacturing a display element according to any one of 1 to 17, wherein the display system is an electrodeposition system.

  19. 19. The display according to 18 above, wherein the counter electrode is operated so as to cause dissolution or precipitation of silver, having an electrolyte containing silver or a compound containing silver in the chemical structure between the counter electrodes. element.

  20. 20. The display element as described in 19 above, wherein the electrolyte contains a mercapto compound or a thioether compound.

  21. 21. The display device as described in 20 above, wherein the mercapto compound or thioether compound is represented by the following general formula (1) or (2).

[Wherein, M represents a hydrogen atom, a metal atom or quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring. n represents an integer of 0 to 5, and R ₁ represents a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group Represents an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, a carboxyl group, a carbonyl group, a sulfonyl group, an amino group, a hydroxy group or a heterocyclic group, and when n is 2 or more, each R ₁ is the same. They may be different from each other or may be linked to each other to form a condensed ring. ]
General formula (2)
R ₂ -S-R ₃
[Wherein R ₂ and R ₃ each represents a substituted or unsubstituted hydrocarbon group. ]
22. 18. A display element manufactured by the method for manufacturing a display element according to any one of 1 to 17, wherein the display system is an electrochromic system using a compound exhibiting electrochromic properties.

  23. 23. The display device as described in 22 above, wherein the compound exhibiting electrochromic properties is a compound represented by the following general formula (3).

[Wherein, R ¹ is — (CH ₂ ) _m — (wherein m represents an integer of 0 or 1 to 10), each an arylene group having up to 14 carbon atoms, a heteroarylene group, or each carbon atom. A branched alkylene group, alkenylene group, or cycloalkylene group of up to several tens, and each arylene group, heteroarylene group, branched alkylene group, branched alkenylene group, or cycloalkylene group is optionally -P (O) (OH) ₂ group - (CH _{2) n} - may have through a group. Moreover, you may substitute arbitrarily. Here, n represents 0 or an integer of 1 to 10. R ² is a group represented by R ³ R ⁴ , wherein R ³ represents — (CH ₂ ) _p — (wherein p represents 0 or an integer of 1 to 10), and R ⁴ Represents a —P (O) (OH) ₂ group, or an aryl group or heteroaryl group having up to 14 carbon atoms, a branched alkyl group, an alkenyl group, or a cycloalkyl group each having up to 10 carbon atoms. . X ₂ ⁻ represents an ion that neutralizes the charge. However, when R ² is — (CH ₂ ) ₂ —P (O) (OH) ₂ , R ¹ is not — (CH ₂ ) _m — (m is 2 or 3). In addition, when R ² is a phenyl group, R ¹ is not — (CH ₂ ) _m — (m is 2). ]
24. 23. The display device as described in 22 above, wherein the compound exhibiting electrochromic properties is a compound represented by the following general formula (4).

[Wherein, R ⁵ represents a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ each represents a hydrogen atom or a substituent. X represents> N—R ⁸ , an oxygen atom or a sulfur atom, and R ⁸ represents a hydrogen atom or a substituent. ]
25. 25. The display element according to any one of 18 to 24, wherein at least one of the counter electrodes is formed on a plastic resin.

  INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for manufacturing a display element that can provide a display element excellent in durability (sealability) and display unevenness resistance without damaging the electrodes, and an electrodeposition method and an electrochromic method obtained thereby. A display element could be provided.

  Hereinafter, details of the display element and the manufacturing method thereof according to the present invention will be described.

  In the method for producing a display element of the present invention, the electrolyte contains a polymer binder and a spacer, and an electrolyte layer is formed on one electrode of the counter electrode using the electrolyte, and the other electrode of the counter electrode is pasted. In the manufacturing method of an electrochemically operated display element that forms a display element together, the average particle size of the spacer and the thickness of the electrolyte layer are substantially equal to each other when the other electrode of the counter electrode is bonded. A layer formed of a thermosetting resin or a photocurable resin (hereinafter also referred to as a sealing agent layer) is formed so as to surround the outer periphery of the electrolyte layer, and the electrolyte layer and the seal A pillar is formed between the material layer and the agent layer. In the present invention, the average particle size of the spacer and the thickness of the electrolyte layer are substantially equal means that the difference between the two is within 5%, preferably within 1%.

  Further, in the method for producing a display element of the present invention, screen printing suitability is imparted by adding a butyral resin as a polymer binder to the electrolyte, and an average particle size corresponding to the gap between the counter electrodes is further increased. By forming an electrolyte layer on the electrode with the spacers mixed by screen printing, there is virtually no movement of the spacer when bonding the electrodes, so the electrode surface is not damaged, and the electrolyte and seal By providing a pillar between the adhesive and the adhesive, the curability and adhesion of the sealing agent due to contact with the electrolyte are not reduced.

  First, the structure of the display element of the present invention will be described with reference to the drawings.

(Basic structure of display element)
In the display element of the present invention, for example, one corresponding counter electrode is provided in an electrodeposition type ED display unit. The electrode A, which is one of the counter electrodes close to the display unit, is provided with a transparent electrode such as an ITO electrode, and the other electrode B is provided with a metal electrode such as a silver electrode. In the ED system, an electrolyte layer having silver or a compound containing silver in the chemical structure is supported between the electrode A and the electrode B, and by applying a voltage of both positive and negative polarity between the counter electrodes, A redox reaction of silver is performed on the electrode 1 and the electrode 2, and a black silver image in a reduced state and a transparent silver state in an oxidized state can be switched reversibly.

  In the display element of the present invention, for example, one corresponding counter electrode is provided in an electrochromic EC display section. The electrode C, which is one of the counter electrodes close to the display portion, is provided with a transparent electrode such as an ITO electrode, and the other electrode D is provided with an electrode having a tin oxide layer doped with antimony on the ITO electrode. An electrolyte layer having an electrochromic dye is provided between the electrode C and the electrode D, and an electrochromic dye oxidation-reduction reaction is performed on the electrode C by applying positive and negative polarities between the counter electrodes. The electrochromic coloring state can be switched reversibly.

  FIG. 1 is a schematic cross-sectional view showing an example of a configuration of a conventional display element to which a pillar according to the present invention is not applied.

  In FIG. 1, the display element 1 is provided with an electrolyte layer 4 including a spacer 3 on one electrode 2 of a counter electrode. The outer peripheral portion of the electrolyte layer 4 is made of a thermosetting resin or a photocurable resin. A sealant layer 5 to be formed is provided, and the other electrode 6 of the counter electrode is bonded to this structure to form a display element. When the display element is configured in such a manner, the electrolyte containing the solvent and the thermosetting resin or photocurable resin forming the sealing agent layer 5 are in direct contact with each other, and as a result, stored for a long period of time. At this time, the electrolyte is deteriorated by the thermosetting resin or the photo-curing resin and peeling between the sealing agent layer and the electrode is likely to occur, resulting in a decrease in display performance and a decrease in sealing performance. Further, after the electrolyte layer 4 and the sealant layer 5 are applied on the electrode 2, when the other electrode 6 is bonded to the upper part thereof, the gap is restricted only by the spacer 3, and the electrode 6 is bonded at the time of bonding. As the electrode moves and the electrolyte spreads, the spacer 3 moves on the electrode 2, and as a result, the surface of the electrode 2 is damaged.

  FIG. 2 is a schematic cross-sectional view showing an example of the configuration of the display element to which the pillar according to the present invention is applied.

  2A, the display element 1 is provided with an electrolyte layer 4 including a spacer 3 on one electrode 2 of a counter electrode, and a thermosetting resin or photocuring is provided on the outer periphery of the electrolyte layer 4. A sealing agent layer 5 formed from a mold resin is provided, and a pillar 7 is provided between the electrolyte layer 4 and the sealing agent layer 5. A display element is formed by bonding the other electrode 6 of the counter electrode on this structure. When the display element is configured in such a manner, the electrolyte containing the solvent and the thermosetting resin or photocurable resin forming the sealing agent layer 5 are not in direct contact, and as a result, stored for a long period of time. In this case, by separating the separation between the sealant layer and the electrode with a pillar, the electrolyte characteristics and sealability are sufficiently maintained. Further, after the electrolyte layer 4, the pillar 7 and the sealant layer 5 are provided on the electrode 2, when the other electrode 6 is bonded to the upper part, the gap is regulated by the pillar 7 and the spacer 3. It is possible to prevent the spacer 3 from moving on the electrode 2 due to the movement of the electrode 6 and the spread of the electrolyte during bonding.

  In the method for manufacturing a display element of the present invention, as shown in FIG. 2, it is preferable that the average particle diameter R of the spacer 3 contained in the electrolyte layer 4 and the maximum height H of the pillar 7 are substantially equal. In the present invention, “substantially equal” means that the difference between the average particle diameter R and the maximum height H of the pillar 7 is within 5%, preferably within 1%.

  Further, in the present invention, a method in which the distance between the counter electrodes is regulated by the average particle diameter R of the spacer 3 or a method in which the distance between the counter electrodes is defined by the maximum height H of the pillar 7 is preferable. The latter is more preferable in consideration of damage prevention.

  Moreover, in the manufacturing method of the display element of this invention, after providing the electrolyte layer 4, the pillar 7, and the sealing agent layer 5 on the electrode 2, when bonding the other electrode 6 on the upper part, the sealing agent layer 5 is attached. The film thickness H2 is preferably larger than the height H of the pillar 7.

  FIG. 2 b shows a configuration in which a plurality of (two in FIG. 2 b) pillars 7 are provided between the electrolyte layer 4 and the sealing agent layer 5.

  By providing a plurality of pillars 7 in this way, when the electrode 6 is coated, excess thermosetting resin or photocurable resin overflows, but this overflow occurs between two adjacent pillars. Trapping the thermosetting resin or the photocurable resin is preferable because contact between the electrolyte layer and the sealing agent can be further prevented.

  Next, each component of the display element of the present invention will be described in more detail.

[Pillar]
The display element manufacturing method of the present invention is characterized in that pillars are formed between the electrolyte layer and the thermosetting or photocurable resin layer.

  The pillar according to the present invention is a structure that prevents contact between the electrolyte and the sealant, and ejects ink that includes a thermosetting resin or photocurable resin that is cured by heat or light by an ink jet recording method. Or a paste containing a thermosetting resin or photocurable resin that is cured by heat or light by screen printing, or by using a photospacer technique used in liquid crystals be able to.

(Electrolyte layer)
The electrolyte layer formed between the counter electrodes according to the present invention is characterized by containing a polymer binder and a spacer, and further contains a white scatterer, an organic solvent, an ionic liquid, a redox active substance, a supporting electrolyte, and the like. It can be added as necessary.

  Hereinafter, each component of the electrolyte layer according to the present invention will be described.

(Polymer binder)
In the electrolyte layer according to the present invention, a polymer binder is used from the viewpoint of increasing the viscosity, and the polymer binder is not particularly limited. For example, a butyral resin, polyvinyl alcohol, polyethylene glycol, polyfluoride is used. It can be selected from various polymer compounds such as vinylidene from the viewpoint of the characteristics of the display element and the viscosity of the electrolyte.

  As the polymer binder according to the present invention, it is preferable to use a butyral resin from the viewpoint of further achieving the object effects of the present invention.

  The butyral resin that can be applied to the present invention is not particularly limited, but from the viewpoint that the objective effect of the present invention can be further exerted, the number of PVA groups represented by (A) is 1) the PVA group, 2) A butyral resin that is 15% or more and 25% or less of the total number [1) +2) +3)] of the PVAc group represented by (B) and 3) the PVB group represented by (C) It is preferable to do.

  The butyral resin according to the present invention is preferably a butyral resin having an average degree of polymerization in the range of 300 or more and 1000 or less, more preferably a butyral resin having an average degree of polymerization of 400 or more and 800 or less.

  The butyral resin according to the present invention can be used by being dissolved by heating after being added to an organic solvent, and the mass ratio of the organic solvent and the butyral resin is preferably in the range of 10: 1 to 2: 1. A preferred range is 10: 1 to 10: 3.

  Specific examples of the butyral resin applicable to the electrolyte layer according to the present invention include, for example, # 3000-1, # 3000-2, # 3000-4, # 3000-K, # 4000- manufactured by Denki Kagaku Kogyo Co., Ltd. 2, # 5000-A, # 5000-D, # 6000-C, # 6000-AS, # 6000-CS, SLEKK series manufactured by Sekisui Chemical Co., Ltd., and the like.

(spacer)
The spacer according to the present invention is a fine particle for controlling the gap between the counter electrodes. For example, a fine sphere made of glass, acrylic resin, silica or the like used for a liquid crystal display or the like is used. Can do. The average particle diameter is preferably in the range of 10 μm or more and 50 μm or less from the viewpoint of dispersion stability in the electrolyte, screen printing suitability, or display characteristics of the device.

(Organic solvent)
As the organic solvent applicable in the electrolyte layer according to the present invention, an organic solvent having a boiling point in the range of 120 to 300 ° C. that can remain in the electrolyte layer without causing volatilization after the electrolyte layer is formed can be used. For example, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, γ-butyl lactone, tetramethyl urea, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 2- (N-methyl) -2-pyrrolidinone, hexamethylphosphortriamide, N-methylpropionamide, N, N-dimethylacetamide, N-methylacetamide, N, N-dimethylformamide, N-methylformamide, butyronitrile, propioni Ril, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2-propanol, 1-propanol, acetic anhydride, ethyl acetate, ethyl propionate, dimethoxyethane, diethoxyfuran, tetrahydrofuran, ethylene Examples include glycol, diethylene glycol, and triethylene glycol monobutyl ether.

  Among the organic solvents, cyclic carboxylic acid esters are preferable. Examples thereof include propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and γ-butyl lactone.

  As other solvents that can be used in the present invention, J.P. A. Riddick, W.M. B. Bunger, T.A. K. Sakano, “Organic Solvents”, 4th ed. , John Wiley & Sons (1986). Marcus, “Ion Solvation”, John Wiley & Sons (1985), C.I. Reichardt, “Solvents and Solvent Effects in Chemistry”, 2nd ed. VCH (1988), G .; J. et al. Janz, R.A. P. T.A. Tomkins, “Nonqueous Electronics Handbook”, Vol. 1, Academic Press (1972).

(White scattered matter)
The electrolyte layer according to the present invention preferably contains a white scatterer.

  The white scattering material referred to in the present invention is any material that can adjust the display color by adding it to the electrolyte layer, preferably an inorganic material, more preferably a metal oxide. Examples of the metal oxide include titanium dioxide (anatase type or rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide and zinc hydroxide, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, Alkaline earth metal salts, talc, kaolin, zeolite, acidic clay, glass and the like can be mentioned.

  In addition, as an organic compound, polyethylene, polystyrene, acrylic resin, ionomer, ethylene-vinyl acetate copolymer resin, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyamide resin, etc. are used alone or in a composite mixture, or in particles. You may use it in the state which has the void which changes a refractive index.

In the present invention, among the coloring materials, titanium dioxide, zinc oxide, and zinc hydroxide are preferably used. In particular, titanium dioxide is used from the viewpoint of preventing coloring at high temperatures and reflectivity of the element due to refractive index. Is more preferable. The titanium dioxide is preferably titanium dioxide that is surface-modified with at least one selected from SiO ₂ , Al ₂ O ₃ and organic substances.

  The white scattering material according to the present invention is added to the mixture of the organic solvent and the butyral resin constituting the electrolyte layer according to the present invention, and dispersed in the electrolyte using a wet pulverizing disperser such as an ultrasonic disperser or a bead mill. Can be used.

  In the present invention, the mass ratio of the organic solvent to the coloring material is preferably in the range of 10: 1 to 1: 1, more preferably 5: 1 to 5: 4.

  The white scattering material according to the present invention is preferably added after the butyral resin is dissolved in an organic solvent or an ionic liquid.

(Silver or a compound containing silver in the chemical structure)
When the display element of the present invention is an ED system, the electrolyte contains silver or a compound containing silver in the chemical structure, and the compound containing silver or silver in the chemical structure in the present invention refers to, for example, It is a generic term for compounds such as silver oxide, silver sulfide, metallic silver, silver colloidal particles, silver halide, silver complex compounds, and silver ions, and the state species of the phase such as solid state, solubilized state in liquid and gas state, The charged state species such as neutral, anionic, and cationic are not particularly limited.

(Mercapto compound, thioether compound)
The electrolyte layer according to the present invention preferably contains a mercapto compound or a thioether compound together with the above-described white scattering material, butyral resin, organic solvent, and the like. It is preferable that it is a compound represented by 1), or that the thioether compound is a compound represented by the general formula (2).

  The mercapto compound represented by the general formula (1) according to the present invention will be described.

In the general formula (1), M represents a hydrogen atom, a metal atom or quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring. n represents an integer of 0 to 5, and R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group Group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryl Represents an oxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, a carboxyl group, a carbonyl group, a sulfonyl group, an amino group, a hydroxy group or a heterocyclic group, and when n is 2 or more, each R ₁ is They may be the same or different, and may be linked together to form a condensed ring.

Examples of the metal atom represented by M in the general formula (1) include Li, Na, K, Mg, Ca, Zn, and Ag. Examples of the quaternary ammonium include NH ₄ , N (CH ₃ ) ₄ , N (C ₄ H ₉ ) ₄ , N (CH ₃ ) ₃ C ₁₂ H ₂₅ , N (CH ₃ ) ₃ C ₁₆ H ₃₃ , N (CH ₃ ) ₃ CH ₂ C ₆ H _{5 and the} like It is done.

  Examples of the nitrogen-containing heterocycle represented by Z in the general formula (1) include tetrazole ring, triazole ring, oxadiazole ring, thiadiazole ring, indole ring, oxazole ring, benzoxazole ring, benzothiazole ring, benzoselena Examples thereof include a sol ring and a naphthoxazole ring.

Examples of the halogen atom represented by R ₁ in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include methyl, ethyl, propyl, i- Examples include propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, etc. Examples of the aryl group include phenyl, naphthyl and the like. Examples of the alkylcarbonamide group include acetylamino, propionylamino, butyroylamino and the like. Examples of the arylcarbonamide group include benzoylamino and the like. Examples of the sulfonamide group include methanesulfonyl. Minosulfonyl, ethanesulfonylamino group and the like, arylsulfonamide groups include, for example, benzenesulfonylamino group, toluenesulfonylamino group and the like, and aryloxy groups include, for example, phenoxy and the like, alkylthio Examples of the group include each group such as methylthio, ethylthio, and butylthio. Examples of the arylthio group include phenylthio group and tolylthio group. Examples of the alkylcarbamoyl group include methylcarbamoyl, dimethylcarbamoyl, Examples include ethyl carbamoyl, diethyl carbamoyl, dibutyl carbamoyl, piperidyl carbamoyl, morpholyl carbamoyl and the like, and aryl carbamoyl groups include, for example, phenyl carbamoyl, methyl phenyl carbamoyl Examples include groups such as vamoyl, ethylphenylcarbamoyl, and benzylphenylcarbamoyl. Examples of the alkylsulfamoyl group include methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, and dibutylsulfamoyl. Examples of each group include moyl, piperidylsulfamoyl, morpholylsulfamoyl, and arylsulfamoyl groups include, for example, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group. Examples of the arylsulfonyl group include phenylsulfonyl and 4-chlorophenylsulfonyl. Examples of each group include p-toluenesulfonyl and the like. Examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl. Examples of the aryloxycarbonyl group include phenoxycarbonyl and the like. Examples of the alkylcarbonyl group include acetyl, propionyl, butyroyl, and the like. Examples of the arylcarbonyl group include a benzoyl group and an alkylbenzoyl group. Examples of the acyloxy group include acetyloxy. , Propionyloxy, butyroyloxy and the like, and examples of the heterocyclic group include oxazole ring, thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, thiadiazole ring, thiazol ring, and the like. Down ring, a triazine ring, a benzoxazole ring, benzothiazole ring, an indolenine ring, benzimidazole benzoselenazole ring, naphthothiazole ring, triazaindolizine ring, diaza indolizine ring, tetraazacyclododecane indolizine ring group, and the like. These substituents further include those having a substituent.

  Next, although the preferable specific example of a compound represented by General formula (1) is shown, this invention is not necessarily limited to these compounds.

  Next, the thioether compound represented by the general formula (2) will be described.

In the general formula (2), R ₂ and R ₃ each represents an alkyl group, an aryl group or a heterocyclic group, and may be the same or different, and may be linked to each other to form a ring. Also good.

Examples of the alkyl group represented by R ₂ and R ₃ in the general formula (2) include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. , Hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include an oxazole ring and an imidazole ring. , Thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, thiadiazole ring, thiazine ring, triazine ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, indolenine ring, benzselenazole ring, naphthothiazole Ring, Triazaindori Down ring, diaza indolizine ring, tetraazacyclododecane indolizine ring group, and the like. These substituents further include those having a substituent.

Next, preferred specific examples of the compound represented by the general formula (2), the present invention but not being limited to these compounds _{2-1: CH 3 SCH 2 CH 2} OH
2-2: HOCH ₂ CH ₂ SCH ₂ CH ₂ OH
2-3: HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH
2-4: HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH
2-5: HOCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ OH
2-6: HOCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OH
2-7: H ₃ CSCH ₂ CH ₂ COOH
2-8: HOOCCH ₂ SCH ₂ COOH
2-9: HOOCCH ₂ CH ₂ SCH ₂ CH ₂ COOH
2-10: HOOCCH ₂ SCH ₂ CH ₂ SCH ₂ COOH
2-11: HOOCCH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ COOH
2-12: HOOCCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH (OH) CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ COOH
_{2-13: HOOCCH 2 CH 2 SCH 2} CH 2 SCH 2 CH (OH) CH (OH) CH 2 SCH 2 CH 2 SCH 2 CH 2 COOH
2-14: H ₃ CSCH ₂ CH ₂ CH ₂ NH ₂
2-15: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
2-16: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
2-17: H ₃ CSCH ₂ CH ₂ CH (NH ₂ ) COOH
2-18: H ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ NH ₂
2-19: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
2-20: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
2-21: HOOC (NH ₂ ) CHCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ CH (NH ₂ ) COOH
2-22: HOOC (NH ₂ ) CHCH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH (NH ₂ ) COOH
2-23: HOOC (NH ₂ ) CHCH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH (NH ₂ ) COOH
2-24: H ₂ N (O═) CCH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ C (═O) NH ₂
2-25: H ₂ N (O═) CCH ₂ SCH ₂ CH ₂ SCH ₂ C (═O) NH ₂
2-26: H ₂ NHN (O═) CCH ₂ SCH ₂ CH ₂ SCH ₂ C (═O) NHNH ₂
2-27: H ₃ C (O═) CNHCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NHC (═O) CH ₃
2-28: H ₂ NO ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SO ₂ NH ₂
2-29: NaO ₃ SCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ SO ₃ Na
2-30: H ₃ CSO ₂ NHCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NHO ₂ SCH ₃
2-31: H ₂ N (NH) CSCH ₂ CH ₂ SC (NH) NH ₂ .2HBr
2-32: H ₂ N (NH) CSCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SC (NH) NH ₂ .2HCl
2-33: H ₂ N (NH) CNHCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NHC (NH) NH ₂ .2HBr
2-34: [(CH ₃ ) ₃ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ N (CH ₃ ) ₃ ] 2 ⁺ · 2Cl ⁻

  The mercapto compound or thioether compound according to the present invention may be used alone or in combination, and the total number of moles of mercapto compound and thioether compound relative to the number of moles of Ag ions in the electrolyte layer. Is preferably in the range of 0.2-2.

(Halogen ion, silver ion concentration ratio)
In the ED display element of the present invention, the molar concentration of halogen ions or halogen atoms contained in the electrolyte is [X] (mol / kg), and silver or silver contained in the electrolyte is contained in the chemical structure. When the total molar concentration of silver is [Ag] (mol / kg), it is preferable that the condition defined by the following formula (1) is satisfied.

Formula (1)
0 ≦ [X] / [Ag] ≦ 0.01
The halogen atom as used in the field of this invention means an iodine atom, a chlorine atom, a bromine atom, and a fluorine atom. When [X] / [Ag] is larger than 0.01, X ⁻ → X ₂ is generated during the redox reaction of silver, and X ₂ easily cross-oxidizes with blackened silver to dissolve blackened silver. Therefore, the molar concentration of halogen atoms is preferably as low as possible relative to the molar concentration of silver. In the present invention, 0 ≦ [X] / [Ag] ≦ 0.001 is more preferable. In the case of adding halogen ions, the halogen species preferably have a total molar concentration of [I] <[Br] <[Cl] <[F] from the viewpoint of improving memory properties.

(Electrolyte-silver salt)
In the ED display element of the present invention, silver iodide, silver chloride, silver bromide, silver oxide, silver sulfide, silver citrate, silver acetate, silver behenate, silver p-toluenesulfonate, mercaptos Known silver salt compounds such as silver salts and silver complexes with iminodiacetic acids can be used. Among these, it is preferable to use, as a silver salt, a compound that does not have a nitrogen atom having coordination properties with halogen, carboxylic acid, or silver, and for example, silver p-toluenesulfonate is preferable.

  The concentration of silver ions contained in the ED electrolyte according to the present invention is preferably 0.2 mol / kg ≦ [Ag] ≦ 2.0 mol / kg. If the silver ion concentration is less than 0.2 mol / kg, it becomes a dilute silver solution, and the driving speed is delayed. If it is greater than 2 mol / kg, the solubility deteriorates, and precipitation tends to occur during low-temperature storage, which is disadvantageous. It is.

[EC display element]
The EC display element of the present invention contains a compound exhibiting electrochromic properties, specifically, an electrochromic dye.

(Electrochromic dye)
The electrochromic dye according to the present invention is not particularly limited as long as it is a compound having electrochromic properties, and specifically, JP-A-62-297382, JP-A-62-286489, and JP-A-3-54528. And dyes described in JP-A-5-224242, JP-A-5-98251, JP-A-2004-01729, JP-A-2000-241835, International Publication No. 2004/066733, and the like.

  In the present invention, among them, a compound having electrochromic properties represented by the general formula (3) and the general formula (4) is preferable.

  First, the compound represented by the general formula (3) will be described.

In the general formula (3), R ¹ is — (CH ₂ ) _m — (where m represents 0 or an integer of 1 to 10), each an arylene group having up to 14 carbon atoms, a heteroarylene group, Alternatively, each is a branched alkylene group, an alkenylene group, or a cycloalkylene group having up to 10 carbon atoms, and each arylene group, heteroarylene group, branched alkylene group, branched alkenylene group, or cycloalkylene group is optionally -P (O ) (OH) ₂ group may be present via a — (CH ₂ ) _n — group. Moreover, you may substitute arbitrarily. Here, n represents 0 or an integer of 1 to 10. R ² is a group represented by R ³ R ⁴ , wherein R ³ represents — (CH ₂ ) _p — (wherein p represents 0 or an integer of 1 to 10), and R ⁴ Represents a —P (O) (OH) ₂ group, or an aryl group or heteroaryl group having up to 14 carbon atoms, a branched alkyl group, an alkenyl group, or a cycloalkyl group each having up to 10 carbon atoms. . X ₂ ⁻ represents an ion that neutralizes the charge. However, when R ² is — (CH ₂ ) ₂ —P (O) (OH) ₂ , R ¹ is not — (CH ₂ ) _m — (m is 2 or 3). In addition, when R ² is a phenyl group, R ¹ is not — (CH ₂ ) _m — (m is 2).

Each of the arylene group, heteroarylene group having up to 14 carbon atoms, branched alkylene group, branched alkenylene group, or cycloalkylene group each having up to 14 carbon atoms represented by R ¹ optionally has a substituent. These groups may be substituted by one or two or more, and when a plurality of groups are substituted, they may be different from each other or the same substituent.

  Examples of these substituents include the following groups.

  Lower alkyl group, lower alkenyl group, phenyl substituted-lower alkyl group, diphenyl substituted-lower alkyl group, phenyl group, phenoxy group, lower alkanoyloxy group, halogen atom, amino group, cyano group, nitro group, lower alkylamino group, Di (lower alkyl) amino group, phenylamino group, lower alkanoylamino group, benzoylamino group, lower alkylsulfonylamino group, phenylsulfonylamino group, lower alkanoyl group, benzoyl group, carboxyl group, lower alkoxycarbonyl group, carbamoyl group, N-lower alkylcarbamoyl group, N, N-di- (lower alkyl) carbamoyl group, ureido group, N-lower alkylureido group, lower alkylsulfonyl group, phenylsulfonyl group, hydroxyl group, lower alkoxy group, Mino group, lower alkylamino group, di (lower alkyl) amino group, lower alkoxy group substituted by halogen atom, carboxyl group or lower alkoxycarbonyl group, alkoxy group having 3 to 7 carbon atoms, and divalent methylene And a dioxy group.

  In addition, the phenyl groups mentioned above, and the phenyl groups contained in the benzoyl group, phenylamino group, etc. are all substituted with lower alkyl groups, lower alkoxy groups, halogen atoms, hydroxy groups, and / or nitro groups. It may be.

Also, the aryl group, heteroaryl group, branched alkyl group, alkenyl group, cycloalkyl group, etc. represented by R ⁴ may be unsubstituted, ^one of which is defined by the group defined as the substituent of R ^1. Alternatively, a plurality of substitutions may be made.

In the general formula (3), as a preferable compound, R ¹ is — (CH ₂ ) _m — (where m represents 1, 2, 3), a phenyl group (— (CH ₂ ) _n — group). P is substituted with a -P (O) (OH) ₂ group, and n represents 1 or 2, and in R ² (represented by R ³ R ⁴ ), R ³ is — (CH ₂ ) _p — (wherein p represents 0, 1, 2, 3), R ⁴ is unsubstituted phenyl or naphthyl, an alkyl group having 1 to 4 carbon atoms, or a halogen atom A phenyl or naphthyl group mono-, di- or tri-substituted by a cyano group, a nitro group, a phenoxy group or a benzoyl group.

X ₂ ⁻ is Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , C ₂ F ₆ NO ₄ S ₂ ⁻ or CF ₃ SO ₃ ⁻ , and particularly preferably Cl ^−. PF ₆ ⁻ .

  Below, the preferable specific example of the electrochromic dye represented by General formula (3) is given.

3-1) 1-phosphonoethyl-1 '-(3-propylphenyl) -4,4'-bipyridinium dichloride 3-2) 1-phosphonoethyl-1'-(3-propylphenyl) -4,4 '-Bipyridinium bis-hexafluorophosphate 3-3) 1-phosphonoethyl-1'-(2,4,6-trimethylphenyl) -4,4'-bipyridinium dichloride 3-4) 1-phosphonoethyl- 1 '-(2,4,6-trimethylphenyl) -4,4'-bipyridinium bis-hexafluorophosphate 3-5) 1-phosphonoethyl-1'-(naphthyl) -4,4'-bipyridinium dichloride 3-6) 1-phosphonoethyl-1 ′-(4-cyanonaphthyl) -4,4′-bipyridinium dichloride 3-7) -Phosphonoethyl-1 '-(4-methylphenyl) -4,4'-bipyridinium dichloride 3-8) 1-phosphonoethyl-1'-(4-cyanophenyl) -4,4'-bipyridinium dichloride 3 -9) 1-phosphonoethyl-1 '-(4-fluorophenyl) -4,4'-bipyridinium dichloride 3-10) 1-phosphonoethyl-1'-(4-phenoxyphenyl) -4,4 ' -Bipyridinium dichloride 3-11) 1-phosphonoethyl-1 '-(4-t-butylphenyl) -4,4'-bipyridinium dichloride 3-12) 1-phosphonoethyl-1'-(2,6- Dimethylphenyl) -4,4'-bipyridinium dichloride 3-13) 1-phosphonoethyl-1 '-(3,5-dimethyl) Phenyl) -4,4′-bipyridinium dichloride 3-14) 1-phosphonoethyl-1 ′-(4-benzophenone) -4,4′-bipyridinium dichloride 3-15) 1-phosphonobenzyl-1 ′-( 3-propylphenyl) -4,4'-bipyridinium dichloride 3-16) 1-phosphonobenzyl-1 '-(3-propylphenyl) -4,4'-bipyridinium bis-hexafluorophosphate 3-17) 1 -Phosphonobenzyl-1 '-(phosphonoethyl) -4,4'-bipyridinium dichloride 3-18) 1-phosphonobenzyl-1'-(2,4-dinitrophenyl) -4,4'-bipyridinium dichloride 3-19) 1-phosphonobenzyl-1 '-(2,4-dinitrophenyl) -4,4'-bipyridinium bis-hexafluorophosphate 3-20) 1-phosphonobenzyl-1 '-(4-phenoxyphenyl) -4,4'-bipyridinium dichloride 3-21) 1-phosphonobenzyl 1 '-(4-phenoxyphenyl) -4,4'-bipyridinium bis-hexafluorophosphate 3-22) 1-phosphonobenzyl-1'-(4-fluorophenyl) -4,4'-bipyridinium dichloride 3 -23) 1-phosphonobenzyl-1 '-(4-methylphenyl) -4,4'-bipyridinium dichloride 3-24) 1-phosphonobenzyl-1'-(2,4,6-trinitrophenyl) -4,4'-bipyridinium dichloride 3-25) 1-phosphonobenzyl-1 '-( Ndyl) -4,4′-bipyridinium dichloride 3-26) 1-phosphonobenzyl-1 ′-(naphthyl) -4,4′-bipyridinium dichloride 3-27) 1-phosphonobenzyl-1 ′-(phenyl) -4,4'-bipyridinium dichloride 3-28) 1-phosphonobenzyl-1 '-(4-cyanophenyl) -4,4'-bipyridinium dichloride 3-29) 1-phosphonobenzyl-1'-(4 -Benzophenone) -4,4'-bipyridinium dichloride 3-30) 1-phosphonobenzyl-1 '-(4-cyanophenyl) -4,4'-bipyridinium dichloride 3-31) 1-phosphonobenzyl-1' -(2,6-dimethylphenyl) -4,4'-bipyridinium dichloride 3-32) 1 -Phosphonobenzyl-1 '-(3,5-dimethylphenyl) -4,4'-bipyridinium dichloride 3-33) 1-phosphonobenzyl-1'-(2,4,6-trimethylphenyl) -4, 4′-Bipyridinium trifluoromethanesulfonimide A method for producing these compounds is described in WO 2004/066773.

  Moreover, as a preferable electrochromic pigment | dye in this invention, the compound represented by the said General formula (4) is mentioned.

In the general formula (4), R ⁵ represents a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ each represent a hydrogen atom or a substituent, and the substituents represented by R ⁵ , R ⁶ and R ⁷ Specific examples of these include, for example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, etc.). ), Alkenyl group, cycloalkenyl group, alkynyl group (for example, propargyl group), glycidyl group, acrylate group, methacrylate group, aromatic group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic group (for example, , Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, Ridazinyl group, selenazolyl group, sriphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group) Etc.), aryloxy group (eg phenoxy group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.) , Sulfonamide groups (for example, methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, benzenesulfonamide group) Amoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group), urethane group ( For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, etc.), acyl group (for example, acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group) Group, benzoyl group, pyridinoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylamino) Nocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group etc.), acylamino group (eg acetylamino group, benzoylamino group, methylureido group etc.), amide group (eg acetamido group, propion) Amide group, butanamide group, hexaneamide group, benzamide group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group, etc.), sulfonamide Group (for example, methylsulfonamide group, octylsulfonamide group, phenylsulfonamide group, naphthylsulfonamide group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butyrate) Amino group, cyclopentylamino group, anilino group, 2-pyridylamino group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, phosphono group (For example, phosphonoethyl group, phosphonopropyl group, phosphonooxyethyl group), oxamoyl group, and the like can be given. Further, these groups may be further substituted with these groups.

R ⁵ is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted 2-hydroxyphenyl group or 4-hydroxyphenyl group.

R ⁶ and R ⁷ are preferably an alkyl group, a cycloalkyl group, an aromatic group, or a heterocyclic group, more preferably one of R ⁶ and R ⁷ is a phenyl group, the other is an alkyl group, and more preferably R ⁶ and R ⁷ are both phenyl groups.

X ₁ is preferably> N—R ⁸ . R ⁸ is preferably a hydrogen atom, an alkyl group, an aromatic group, a heterocyclic group, or an acyl group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or acyl. It is a group.

  Specific examples of the electrochromic dye represented by the general formula (4) are shown below, but the present invention is not limited to these exemplified compounds.

[Thickener added with electrolyte]
In the display element of the present invention, a thickener can be used in the electrolyte layer in addition to the butyral resin according to the present invention as long as the object effect of the present invention is not impaired. For example, gelatin, gum arabic, hydroxyethyl cellulose , Hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly ( Methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (esters), poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly ( Epoxides), poly (carbonates) G), cellulose esters, poly (amides), as the hydrophobic transparent binder, cellulose acetate, cellulose acetate butyrate, polyesters, polycarbonates, polyacrylic acid, and polyurethane.

(Formation of electrolyte layer)
The electrolyte layer according to the present invention is preferably formed by a screen printing method. In the screen printing method, a screen on which a predetermined pattern is formed is placed on an electrode surface of a substrate, and an electrolyte solution is applied on the screen. In this method, the average particle diameter of spacers contained in the electrolyte and the thickness of the electrolyte layer when the electrolyte layer is formed by screen printing are substantially the same.

  After forming the electrolyte layer, the other electrode of the counter electrode is attached. From the viewpoint of avoiding mixing of bubbles at the time of bonding, it is preferable to bond in a vacuum state.

[Other components]
In the display element of the present invention, in addition to the above-described constituent elements, various constituent layers can be provided as necessary.

(Porous electrode containing metal oxide)
In the display element of the present invention, a porous electrode containing a metal oxide can also be used.

  In the display element of the present invention, the surface of the counter electrode that is not on the image observation side is protected by a porous electrode containing a metal oxide, so that silver or silver on the surface that is not on the image observation side has a chemical structure. As a result of finding that the oxidation-reduction reaction of the compound contained in the compound is carried out on or in the porous electrode containing the metal oxide, the choice of electrode types that are not on the image observation side is expanded and the durability is improved. Can be made.

  In the present invention, examples of the metal oxide constituting the porous electrode include titanium oxide, silicon oxide, zinc oxide, tin oxide, Sn-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and fluorine-doped tin oxide. (FTO), aluminum-doped zinc oxide and the like, or a mixture thereof.

The porous electrode is formed by binding or contacting a plurality of fine particles of the metal oxide. The average particle diameter of the metal oxide fine particles is preferably 5 nm to 10 μm, more preferably 20 nm to 1 μm. The specific surface area of the metal oxide fine particles is preferably ^{1 × 10 -3 ~1 × 10 2} m 2 / g by a simple BET method, more preferably at 1 × 10 ^-2 ~10m ² / g . In addition, the metal oxide fine particles may have any shape such as an indefinite shape, a needle shape, a spherical shape, or the like.

  As a method for forming or binding metal oxide fine particles, a known sol-gel method or sintering method can be employed. For example, 1) Journal of the Ceramic Society of Japan, 102, 2, p200 (1994), 2 ) Ceramics Association Journal 90, 4, p157, 3) J. of Non-Cryst. Solids, 82, 400 (1986) and the like. In addition, a method of obtaining a porous electrode by dispersing titanium oxide dendrimer particles prepared by a vapor phase method on a solution and applying the particles on a substrate and drying at a temperature of about 120 to 150 ° C. to remove the solvent is used. You can also. The metal oxide fine particles are preferably bound, and preferably have a resistance of 0.1 g or more, preferably 1 g or more with a continuous load type surface property measuring instrument (for example, a scratch tester).

  Porous as used in the present invention refers to a penetrating state in which a porous electrode is disposed, a potential difference is applied between the counter electrodes, and a dissolution and precipitation reaction of silver can occur, and the ionic species can move within the porous electrode. Say.

(Electronic insulation layer)
In the display element of the present invention, an electrical insulating layer can be provided.

  The electronic insulating layer applicable to the present invention may be a layer having both ionic conductivity and electronic insulating properties. For example, a solid electrolyte membrane in which a polymer or salt having a polar group is formed into a film, electronic insulating properties And a porous solid body having a low relative dielectric constant, such as a silicon-containing compound, and the like.

  As a method for forming a porous film, a sintering method (fusion method) (particulate fusion of polymer fine particles or inorganic particles by using a binder, etc., and utilizing pores formed between particles), extraction method ( After forming a constituent layer with a solvent-soluble organic or inorganic substance and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved with the solvent to obtain pores), and the polymer is heated or degassed Known forming methods such as a foaming method in which foaming is performed, a phase change method in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent, and a radiation irradiation method in which pores are formed by radiating various types of radiation Can be used. Specifically, Japanese Patent Application Laid-Open Nos. 10-30181, 2003-107626, 7-95403, Japanese Patent Nos. 2635715, 2849523, 29987474, 30664426, and 3464513. No. 3,483,464, No. 3535942, No. 30622203, and the like.

[Other additives]
Examples of the constituent layers of the display element of the present invention include auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, a backing layer, and a tin oxide porous layer. Includes various chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high-boiling solvents, antifoggants, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixtures Inhibitors, formalin scavengers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, UV absorbers, anti-irradiation dyes, filter light absorption dyes, antibacterial agents, polymer latex, heavy metals, An antistatic agent, a matting agent, etc. can be contained as needed.

  More specifically, these additives described above are described in detail in Research Disclosure (hereinafter abbreviated as RD), Volume 176 Item / 17643 (December 1978), Volume 184, Item / 18431 (August 1979), Volume 187. Item / 18716 (November 1979) and Volume 308 Item / 308119 (December 1989).

  The types of compounds and their descriptions shown in these three research disclosures are listed below.

Additive RD17643 RD18716 RD308119
Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 96 III
Sensitizing dye 23 IV 648-649 996-8 IV
Desensitizing dye 23 IV 998 IV
Dye 25-26 VIII 649-650 1003 VIII
Development accelerator 29 XXI 648 Upper right Anti-fogging agent / stabilizer
24 IV 649 Upper right 1006-7 VI
Brightener 24 V 998 V
Hardener 26 X 651 Left 1004-5 X
Surfactant 26-7 XI 650 Right 1005-6 XI
Antistatic agent 27 XII 650 Right 1006-7XIII
Plasticizer 27 XII 650 Right 1006 XII
Slipper 27 XII
Matting agent 28 XVI 650 Right 1008-9 XVI
Binder 26 XXII 1003-4 IX
Support 28 XVII 1009 XVII
(Layer structure)
The constituent layers between the counter electrodes of the display element of the present invention will be further described.

As a constituent layer according to the display element of the present invention, a constituent layer containing a hole transport material can be provided. Examples of hole transport materials include aromatic amines, triphenylene derivatives, oligothiophene compounds, polypyrroles, polyacetylene derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polythiophene derivatives, polyaniline derivatives, polytoluidine derivatives, CuI, CuSCN CuInSe ₂ , Cu (In, Ga) Se, CuGaSe ₂ , Cu ₂ O, CuS, CuGaS ₂ , CuInS ₂ , CuAlSe ₂ , GaP, NiO, CoO, FeO, Bi ₂ O ₃ , MoO ₂ , Cr ₂ O ₃ Etc.

(substrate)
In the display element of the present invention, it is preferable that at least one of the counter electrodes is formed on a plastic substrate.

  Examples of the substrate that can be used in the present invention include polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene dinaphthalene dicarboxylate, polyethylene naphthalates, polyvinyl chloride, polyimide, and polyvinyl acetal. Synthetic plastic films such as polystyrene can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained, for example, by the methods described in JP-A Nos. 62-117708, 1-46912 and 1-178505. Further, a metal substrate such as stainless steel, a paper support such as baryta paper and resin coated paper, and a support provided with a reflective layer on the plastic film, supported by JP-A-62-253195 (pages 29-31) The thing described as a body is mentioned. RDNo. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879 can also be preferably used. As these supports, those having resistance to curling due to heat treatment of Tg or less as in US Pat. No. 4,141,735 can be used. Further, the surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and other constituent layers. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Furthermore, the support body described in pages 44 to 149 of publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) can also be used. Furthermore, RDNo. 308119, page 1009, Product Licensing Index, Volume 92, P108, “Supports”, and the like. In addition, a glass substrate or an epoxy resin kneaded with glass can be used.

(electrode)
In the display element of the present invention, it is preferable that at least one of the counter electrodes is a transparent electrode. The transparent electrode is not particularly limited as long as it is transparent and conducts electricity. For example, Indium Tin Oxide (ITO: Indium Tin Oxide), Indium Zinc Oxide (IZO: Indium Zinc Oxide), Fluorine Doped Tin Oxide (FTO), Indium Oxide, Zinc Oxide, Platinum, Gold, Silver, Rhodium, Copper, Examples thereof include chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide). In order to form the electrode in this manner, for example, an ITO film may be vapor-deposited on the substrate by a sputtering method or the like, or an ITO film may be formed on the entire surface and then patterned by a photolithography method. The surface resistance value is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. The thickness of the transparent electrode is not particularly limited, but is generally 0.1 to 20 μm.

(Display element driving method)
In the ED display element of the present invention, it is preferable to perform a driving operation in which silver black is deposited by applying a voltage equal to or higher than the precipitation overvoltage and silver black is continuously precipitated by applying a voltage lower than the precipitation overvoltage. By performing this driving operation, the writing energy can be reduced, the driving circuit load can be reduced, and the writing speed as a screen can be improved. It is generally known that overvoltage exists in electrode reactions in the electrochemical field. For example, overvoltage is described in detail on page 121 of “Introduction to Chemistry of Electron Transfer—Introduction to Electrochemistry” (published by Asakura Shoten in 1996). Since the display element of the present invention can also be regarded as an electrode reaction between the electrode and silver in the electrolyte, it can be easily understood that overvoltage exists even in silver dissolution precipitation. Since the magnitude of the overvoltage is governed by the exchange current density, it is possible to continue silver black precipitation by applying a voltage equal to or lower than the precipitation overvoltage after the formation of silver black as in the present invention. However, it is presumed that electron injection can be easily performed with little excess electric energy.

  The driving operation of the display element of the present invention may be simple matrix driving or active matrix driving. The simple matrix driving in the present invention is a driving method in which a current is sequentially applied to a circuit in which a positive line including a plurality of positive electrodes and a negative electrode line including a plurality of negative electrodes are opposed to each other in a vertical direction. Say that. By using simple matrix driving, there is an advantage that the circuit configuration and driving IC can be simplified and manufactured at low cost. The active matrix drive is a system in which scanning lines, data lines, and current supply lines are formed in a grid pattern, and are driven by TFT circuits provided in each grid pattern. Since switching can be performed for each pixel, there are merits such as gradation and memory function. For example, a circuit described in FIG. 5 of JP-A-2004-29327 can be used.

When full color display is performed by the EC display element of the present invention,
1. A method of displaying a plurality of colors by stacking a plurality of electrochromic display elements that develop and erase colors in different colors such as yellow, magenta, cyan, red, green, blue, and black,
2. A method of allowing a plurality of colors to be displayed by arranging a porous layer containing titanium oxide adsorbed with an electrochromic dye that develops and decolors in different color tones, between the opposing electrodes;
3. Examples include a method of allowing a plurality of colors to be displayed by adsorbing an electrochromic dye that develops and decolors in different color tones to a porous layer containing the same titanium oxide.

  In the case of 3, the electrochromic dye must have a threshold value. As a method for providing the threshold value, voltage or charge amount in the color developing or decoloring direction or voltage hysteresis in the color developing or decoloring direction is set for each dye. The method of changing to is mentioned.

  The active matrix drive in the EC display device of the present invention is a method in which scanning lines, data lines, and current supply lines are formed in a grid pattern and are driven by a TFT circuit provided in each grid pattern. Since switching can be performed for each pixel, there are advantages such as gradation and memory function. For example, the circuit described in FIG. 5 of Japanese Patent Application Laid-Open No. 2004-29327, “Electrochromic Display” (published by 1991 Sangyo Tosho Co., Ltd.) ) 77-102.

  In the present invention, the tin oxide porous layer of the electrochromic display element is preferably connected to a pixel circuit used for active matrix driving via one of the counter electrodes, and is in contact with the drain of the switching transistor. Because of this, the counter electrode side having a porous layer containing titanium oxide adsorbed with an electrochromic dye is in a disconnected state, so that current leakage is less likely to occur and color misregistration is less likely to occur during color display. There is.

  In an actual pixel circuit, in addition to coloring driving, transistors related to driving such as attenuation and erasing, and power supply lines therefor are mounted. For example, an equivalent circuit described in FIG. 8 of Japanese Patent Application Laid-Open No. 2004-29327 is shown. The connection is made by making contact as described above, but the effect is exactly the same.

[Product application]
The display element of the present invention can be used in an electronic book field, an ID card field, a public field, a traffic field, a broadcast field, a payment field, a distribution logistics field, and the like. Specifically, keys for doors, student ID cards, employee ID cards, various membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railway cards, bus cards, Cash cards, credit cards, highway cards, driver's licenses, hospital examination cards, electronic medical records, health insurance cards, Basic Resident Registers, passports, electronic books, etc.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of electrolyte solution >>
(Preparation of electrolyte solution 1)
In 2.5 g of dimethyl sulfoxide (abbreviated as DMSO in Table 1), 75 mg of silver tosylate and 150 mg of the following compound 1 were added and dissolved by heating to obtain an electrolyte solution 1.

(Preparation of electrolyte solution 2)
In 2.5 g of dimethyl sulfoxide, 500 mg of compound 2 (polyethylene oxide having an average molecular weight of 200,000), 1.2 g of titanium dioxide CR-90 manufactured by Ishihara Sangyo Co., Ltd., 100 mg of silver tosylate, 200 mg of 1 was added and dissolved by heating to obtain an electrolyte solution 2.

(Preparation of electrolyte solution 3)
In 2.5 g of dimethyl sulfoxide, 500 mg of compound B-1 (butyral resin having an average degree of polymerization of 1200 and a polyvinyl alcohol ratio of 10%), 1.2 g of titanium dioxide CR-90 manufactured by Ishihara Sangyo Co., Ltd., and tosyl 100 mg of acid silver and 200 mg of Compound 1 were added and dissolved by heating to obtain an electrolyte solution 3.

(Preparation of electrolyte solution 4)
In 2.5 g of dimethyl sulfoxide, 500 mg of compound B-2 (# 300-1, manufactured by Denki Kagaku Kogyo Co., Ltd., butyral resin having an average polymerization degree of 600 and a polyvinyl alcohol ratio of 18%), titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. 1.2 g of CR-90, 100 mg of silver tosylate, and 200 mg of the following compound 3 were added and dissolved by heating to obtain an electrolyte solution 4.

(Preparation of electrolyte solution 5)
In the preparation of the electrolytic solution 4, an electrolytic solution 5 was obtained in the same manner except that the following compound 4 was used instead of the compound 3.

<Production of electrode>
(Production of electrode 1)
An ITO film having a pitch of 145 μm and an electrode width of 130 μm was formed on a 10 cm × 10 cm glass substrate having a thickness of 1.5 mm according to a known method to obtain a transparent electrode (electrode 1).

(Preparation of electrode 2)
A silver-palladium electrode (electrode 2) having an electrode thickness of 0.8 μm, a pitch of 145 μm, and an electrode interval of 130 μm is formed on a glass substrate having a thickness of 1.5 mm and a size of 10 cm × 10 cm by using a known method. Got.

<< Production of display element >>
(Preparation of display element 1)
The electrode 1 is pasted on the electrode 2 bordered with an epoxy-based ultraviolet curable resin (sealant layer) containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10% and heated. An empty cell was produced by pressing. The electrolyte solution 1 was vacuum-injected into the empty cell, and the injection port was sealed with an epoxy-based ultraviolet curable resin to produce a display element 1.

(Preparation of display element 2)
On the periphery of the electrode 2 bordered with an epoxy-based ultraviolet curable resin (sealant layer) containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10%, the glass spherical bead shape The electrolyte solution 2 in which the spacer was mixed so that the volume fraction was 10% was injected with a dispenser, allowed to stand for 5 minutes, and then the electrode 1 was bonded in a vacuum state and heated and pressed to produce the display element 2.

(Preparation of display element 3)
On the periphery of the electrode 2 bordered with an epoxy-based ultraviolet curable resin (sealant layer) containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10%, the glass spherical bead shape Electrolyte solution 3 mixed so that the spacer has a volume fraction of 10% is applied by screen printing to a film thickness of 5 μm to form an electrolyte layer, and after standing for 5 minutes, electrode 1 is applied in a vacuum state. The display element 3 was produced by pasting and heating and pressing.

(Preparation of display element 4)
In the production of the display element 3, a pillar 1 having a width of 10 μm and a height of 40 μm is used on the inner side of the sealant layer, as shown in FIG. A display element 4 was produced in the same manner except that it was formed by patterning by screen printing.

(Preparation of display element 5)
In the production of the display element 4, the display element 5 is similarly formed except that the second pillar 2 is further formed at an interval of 5 μm inside the formed pillar 1 as shown in FIG. Was made.

(Preparation of display element 6)
A display element 6 was produced in the same manner as in the production of the display element 5 except that the electrolyte solution 4 was used instead of the electrolyte solution 3.

(Preparation of display element 7)
In the production of the display element 6, the same applies except that the average particle diameter of the glass spherical bead spacer added to the sealant layer and the electrolyte solution is changed to 5 μm, and the heights of the pillars 1 and 2 are changed to 5 μm, respectively. Thus, a display element 7 was produced.

(Preparation of display element 8)
In the production of the display element 6, the same applies except that the average particle diameter of the glass spherical bead spacer added to the sealant layer and the electrolyte solution is changed to 60 μm, and the heights of the pillars 1 and 2 are changed to 60 μm, respectively. Thus, the display element 8 was produced.

(Preparation of display element 9)
A display element 9 was produced in the same manner as in the production of the display element 5 except that the electrolyte solution 5 was used instead of the electrolyte solution 3.

(Preparation of display element 10)
In the production of the display element 9, the display element 10 was produced in the same manner except that the height of the pillars 1 and 2 was changed to 30 μm.

  Table 1 shows configurations of the manufactured display elements 1 to 10.

<< Evaluation of display element >>
(Evaluation of electrode surface damage)
Each display element produced above is carefully disassembled and the electrode 2 is taken out. After the electrode 2 taken out is washed with pure water and ethanol, the surface of the electrode 2 obtained by heating and drying at 60 ° C. for 1 hour is obtained. The state was observed with an optical microscope to determine the presence or absence of damage.

(Evaluation of display unevenness resistance)
Each display element produced above is stored for 30 days in an environment of 25 ° C., then a voltage of 1.5 V is applied for 1.5 seconds to display white, and a voltage of −1.5 V is applied for 0.5 seconds. The display of gray is repeated 1000 times, and the reflectance at 550 nm at any five locations of the display element is measured with a spectrocolorimeter CM-3700d manufactured by Konica Minolta Sensing Co., Ltd., and the maximum and minimum values of the reflectance are measured. The difference was calculated. The calculated difference in reflectance was taken as ΔR _Glay . Here, the smaller ΔR _Glay is, the better the display unevenness resistance is.

(Durability evaluation)
Each of the display devices prepared above was sealed at 1 ° C, 2 hours, 3 hours, 6 hours, 12 hours, 1 day, 2 days, 3 days, respectively, in an environment of 90 ° C. The presence or absence of peeling was visually observed, and the time for peeling of the sealing agent layer was determined.

  The results obtained as described above are shown in Table 2.

  As is clear from the results shown in Table 2, the display element 1 using the electrolyte solution 1 that does not contain a polymer binder causes a large amount of display unevenness by repeated driving. Further, it can be seen that when the display elements 2 and 3 are bonded to each other, the electrolyte solution containing a spacer spreads on the electrode 2 so that the surface of the electrode 2 is damaged.

  On the other hand, in the display elements 4 to 10 which are provided with the pillar according to the present invention and are formed by the electrolyte solution having the polymer binder and the spacer, the electrolyte does not substantially spread on the electrode 2 when the electrodes 1 and 2 are bonded together. Therefore, the spacer does not damage the surface of the electrode 2, and the electrolyte layer and the sealant layer are separated by pillars, so that it is understood that the durability is excellent.

Example 2
<< Preparation of electrolyte solution >>
(Preparation of electrolyte solution 6)
In γ-butyrolactone (abbreviated as γBL in Table 3), 50 mmol / L of Ex1 below and 1 mmol / L of compound 5 (lithium perchlorate) were added and dissolved by heating to obtain an electrolyte solution 6.

(Preparation of electrolyte solution 7)
In γ-butyrolactone, 20% by mass of the compound 2, 40% by mass of titanium dioxide CR-90 manufactured by Ishihara Sangyo Co., Ltd., 50 mmol / L of Ex1 below, and 1 mmol / L of the compound 5 were added and dissolved by heating. Thus, an electrolyte solution 7 was obtained.

(Preparation of electrolyte solution 8)
In the preparation of the electrolyte solution 7, an electrolyte solution 8 was prepared in the same manner except that the compound B-2 was used instead of the compound 2.

(Preparation of electrolyte solution 9)
In the preparation of the electrolyte solution 8, an electrolyte solution 9 was prepared in the same manner except that the following Ex-2 was used in place of the oxidation-reduction compound Ex1.

(Preparation of electrolyte solution 10)
In the preparation of the electrolyte solution 9, an electrolyte solution 10 was prepared in the same manner except that Exemplified Compound 3-3 was used instead of Ex2 which is a redox compound.

(Preparation of electrolyte solution 11)
In the preparation of the electrolyte solution 9, an electrolyte solution 11 was prepared in the same manner except that Exemplified Compound 3-15 was used instead of Ex2 which is a redox compound.

(Preparation of electrolyte solution 12)
In the preparation of the electrolyte solution 9, an electrolyte solution 12 was prepared in the same manner except that Exemplified Compound 2-107 was used instead of Ex2 which is a redox compound.

(Preparation of electrolyte solution 13)
In the preparation of the electrolyte solution 9, an electrolyte solution 13 was prepared in the same manner except that Exemplified Compound 2-109 was used instead of Ex2 which is a redox compound.

<Production of electrode>
(Preparation of electrode 3)
A dispersion of titanium dioxide (average primary particle size 30 nm) dispersed in terpineol was applied on the ITO electrode and baked at 400 ° C. for 1 hour to form a porous titanium oxide layer (dry film thickness 10 μm). Obtained.

(Preparation of electrode 4)
A tin oxide (average primary particle size: 30 nm) dispersion doped with antimony dispersed in terpineol on an ITO electrode is applied and baked at 400 ° C. for 1 hour to form a tin oxide porous layer (dry film thickness 10 μm). Then, the electrode 4 was produced.

<< Production of display element >>
(Preparation of display element 11)
The electrode 3 is bonded to the periphery of the electrode 4 bordered with an epoxy-based ultraviolet curable resin (sealant layer) containing 10% glass spherical bead spacers with an average particle diameter of 40 μm as a volume fraction, and heated. An empty cell was produced by pressing. The electrolytic solution 6 was vacuum-injected into the empty cell, and the injection port was sealed with an epoxy-based ultraviolet curable resin, whereby the display element 11 was produced.

(Preparation of display element 12)
The glass spherical bead spacer has a volume fraction on the electrode 4 whose peripheral portion is bordered with an epoxy-based ultraviolet curable resin containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10%. As a result, the electrolyte 7 mixed so as to be 10% was injected with a dispenser, allowed to stand for 5 minutes, and then the electrode 3 was bonded in a vacuum state and heated and pressed to produce a display element 12.

(Preparation of display element 13)
The glass spherical bead spacer has a volume fraction on the electrode 4 whose peripheral portion is bordered with an epoxy-based ultraviolet curable resin containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10%. As a result, the electrolyte layer 8 mixed to 10% is formed by screen printing so as to have a film thickness of 40 μm, and left to stand for 5 minutes. 13 was produced.

(Preparation of display element 14)
In the production of the display element 13, a pillar 1 having a width of 10 μm and a height of 40 μm is used on the inner side of the sealant layer, as shown in FIG. A display element 14 was produced in the same manner except that it was formed by patterning by screen printing.

(Preparation of display element 15)
In the production of the display element 14, the display element 15 is similarly formed except that the second pillar 2 is formed at an interval of 5 μm inside the formed pillar 1 as shown in FIG. Was made.

(Production of display elements 16 to 20)
In the production of the display element 15, display elements 16 to 20 were produced in the same manner except that the electrolyte solutions 9 to 13 were used in place of the electrolyte solution 8, respectively.

  Table 3 shows the configuration of the manufactured display elements 11 to 20.

<< Evaluation of display element >>
(Evaluation of electrode surface damage)
Each display element produced above is carefully disassembled and the electrode 4 is taken out. After the electrode 4 taken out is washed with pure water and ethanol, the surface of the electrode obtained by heating and drying at 60 ° C. for 1 hour is obtained. The state was observed with an optical microscope, and the presence or absence of damage was visually determined.

(Evaluation of display unevenness resistance)
Each of the display devices prepared above was stored for 30 days in an environment of 25 ° C., then, 1.5 V voltage application for 1.5 seconds and −1.5 V voltage application for 0.5 seconds were repeated 1000 times. Reflection at a wavelength when the reflection spectrum of any five locations of the display element is measured with a spectrocolorimeter CM-3700d manufactured by Konica Minolta Sensing Co., Ltd., and the maximum reflectance of the color tone displayed on each display element is taken. The difference between the maximum and minimum rates was calculated. The calculated reflectance difference ΔR _Color is obtained, and the smaller this ΔR _Color , the better the display unevenness resistance.

(Durability evaluation)
Durability was evaluated in the same manner as in the method described in Example 1.

  Table 4 shows the results obtained as described above.

  As is apparent from the results shown in Table 4, even in the EC display element, the display element 11 using the electrolyte solution 6 containing no polymer binder causes a large amount of display unevenness by repeated driving. Further, it can be seen that when the display elements 12 and 13 are bonded to the electrode 3 and the electrode 4, the surface of the electrode 4 is damaged by the electrolyte solution containing the spacer spreading on the electrode 4.

  On the other hand, in the display elements 14 to 20 which are provided with the pillar according to the present invention and are formed of an electrolyte solution having a polymer binder and a spacer, the electrolyte does not substantially spread on the electrode 4 when the electrodes 3 and 4 are bonded together. Therefore, the spacer does not damage the surface of the electrode 4, and the electrolyte layer and the sealant layer are separated by pillars, so that it is understood that the durability is excellent.

It is a schematic sectional drawing which shows an example of a structure of the display element of a conventional system. It is a schematic sectional drawing which shows an example of a structure of the display element to which the pillar which concerns on this invention is applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display element 2, 6 Electrode 3 Spacer 4 Electrolyte layer 5 Sealing agent layer 7 Pillar

Claims (25)

An electrochemical method in which an electrolyte contains a polymer binder and a spacer, an electrolyte layer is formed on one electrode of the counter electrode using the electrolyte, and the other electrode of the counter electrode is bonded to form a display element In the method of manufacturing a display element that operates at the same time, when the other electrode of the counter electrode is bonded, the average particle diameter of the spacer is substantially equal to the film thickness of the electrolyte layer. A thermosetting resin or photocurable resin layer is formed so as to surround the outer periphery, and a pillar is formed between the electrolyte layer and the thermosetting or photocurable resin layer. A method for manufacturing a display element. The method for manufacturing a display element according to claim 1, wherein at least two pillars are formed between the electrolyte layer and the thermosetting resin or photocurable resin layer. The method for manufacturing a display element according to claim 1, wherein a distance between the counter electrodes is determined by an average particle diameter of a spacer contained in the electrolyte layer. The method for manufacturing a display element according to claim 1, wherein a distance between the counter electrodes is determined by a height of the pillar. 5. The method for manufacturing a display element according to claim 1, wherein an average particle diameter of a spacer contained in the electrolyte layer is substantially equal to a maximum height of the pillar. The film thickness of the layer of the said thermosetting resin or photocurable resin is larger than the height of the said pillar when bonding the two said counter electrodes, The any one of Claims 1-5 characterized by the above-mentioned. The manufacturing method of the display element of description. The overflowed thermosetting resin or photocurable resin is trapped between two adjacent pillars when the counter electrode is bonded. 7. Of manufacturing the display element. 8. The method for manufacturing a display element according to claim 1, wherein a method of forming an electrolyte layer on one electrode of the counter electrode using the electrolyte is a screen printing method. 9. The method for manufacturing a display element according to claim 1, wherein the spacer has an average particle size of 10 μm or more and 50 μm or less. The method for manufacturing a display element according to claim 1, wherein the polymer binder is a butyral resin. The said electrolyte layer contains cyclic carboxylic acid esters as a solvent, The manufacturing method of the display element of any one of Claims 1-10 characterized by the above-mentioned. The method for producing a display element according to claim 10 or 11, wherein an average degree of polymerization of the butyral resin is 300 or more and 1000 or less. The method for producing a display element according to claim 10 or 11, wherein an average polymerization degree of the butyral resin is 400 or more and 800 or less. In the butyral resin, the number of PVA groups represented by the following (A) is 1) the PVA group, 2) the PVAc group represented by the following (B), and 3) the PVB group represented by the following (C). The method for manufacturing a display element according to claim 10, wherein the total number of the display elements is 15% or more and 25% or less.

[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. ] The method for manufacturing a display element according to claim 10, wherein a mass ratio of a solvent and a butyral resin constituting the electrolyte layer is in a range of 10: 1 to 2: 1. . The method for manufacturing a display element according to claim 1, wherein the electrolyte layer contains a white scattering material. The method for manufacturing a display element according to claim 16, wherein the white scattering material is titanium dioxide whose surface is modified with at least one selected from SiO ₂ , Al ₂ O ₃ and an organic material. A display element manufactured by the method for manufacturing a display element according to claim 1, wherein the display system is an electrodeposition system. 19. The counter electrode according to claim 18, wherein the counter electrode has an electrolyte containing silver or a compound containing silver in a chemical structure between the counter electrodes, and the counter electrode is driven so as to cause dissolution and precipitation of silver. Display element. The display element according to claim 19, wherein the electrolyte contains a mercapto compound or a thioether compound. 21. The display element according to claim 20, wherein the mercapto compound or thioether compound is represented by the following general formula (1) or (2).

(In the formula, M represents a hydrogen atom, a metal atom or quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring. N represents an integer of 0 to 5, and R ₁ represents a halogen atom, an alkyl group, an aryl group, an alkyl group. Carboxamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, aryl Sulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, acyloxy group, carboxyl group, carbonyl group, sulfonyl group, a It represents an amino group, hydroxy group or a heterocyclic group, when n is 2 or more, each of R ₁ may be the same, or different, may form a condensed ring by combining to each other. )
Formula (2) R ₂ —S—R ₃
(In the formula, R ₂ and R ₃ each represent a substituted or unsubstituted hydrocarbon group.) A display element manufactured by the method for manufacturing a display element according to claim 1, wherein the display system is an electrochromic system using a compound exhibiting electrochromic properties. The display element according to claim 22, wherein the compound exhibiting electrochromic properties is a compound represented by the following general formula (3).

[Wherein, R ¹ is — (CH ₂ ) _m — (wherein m represents an integer of 0 or 1 to 10), each an arylene group having up to 14 carbon atoms, a heteroarylene group, or each carbon atom. A branched alkylene group, alkenylene group, or cycloalkylene group of up to several tens, and each arylene group, heteroarylene group, branched alkylene group, branched alkenylene group, or cycloalkylene group is optionally -P (O) (OH) ₂ group - (CH _{2) n} - may have through a group. Moreover, you may substitute arbitrarily. Here, n represents 0 or an integer of 1 to 10. R ² is a group represented by R ³ R ⁴ , wherein R ³ represents — (CH ₂ ) _p — (wherein p represents 0 or an integer of 1 to 10), and R ⁴ Represents a —P (O) (OH) ₂ group, or an aryl group or heteroaryl group having up to 14 carbon atoms, a branched alkyl group, an alkenyl group, or a cycloalkyl group each having up to 10 carbon atoms. . X ₂ ⁻ represents an ion that neutralizes the charge. However, when R ² is — (CH ₂ ) ₂ —P (O) (OH) ₂ , R ¹ is not — (CH ₂ ) _m — (m is 2 or 3). In addition, when R ² is a phenyl group, R ¹ is not — (CH ₂ ) _m — (m is 2). ] The display element according to claim 22, wherein the compound exhibiting electrochromic properties is a compound represented by the following general formula (4).

[Wherein, R ⁵ represents a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ each represents a hydrogen atom or a substituent. X represents> N—R ⁸ , an oxygen atom or a sulfur atom, and R ⁸ represents a hydrogen atom or a substituent. ] The display element according to any one of claims 18 to 24, wherein at least one of the counter electrodes is formed on a plastic resin.

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